Light sensitive photographic materials



Patented Feb. 5, 1945 2,368,647

UNITED STATES PATENT OFFICE LIGHT SENSITIVE PHOTOGRAPH) MATERIALS Paul Daniel Dreyfuss, Hollywood, Calif., assignor go (ilgmogen, Incorporated, a corporation No Drawing. Application September 9, 1942, Serial No. 457,755. In Great Britain July 12,

8 Claims. (01.95 4) V This application is a continuation-impart 0! Compounds suitable for carrying out theprocmy application 8. N. 284,102, iiled July 12, 1939. ess of the present invention are, ior example, the

It is already known to flx soluble dyes containbiguanides or dibiguanides derived from ming a sulphonic or carboxylic group for phophenylene-diamine, p-phenylenediamine, 1,8-

tographic purposes by precipitating them with 6 naphthalene diamine, the dibiguanides derived precipitating agents of basic character. As such from benzidine, o-tolidine, o-dianisidine, m-diprecipitating agents, it has been proposed to emchlorbenzidine, naphthidine, p,p'-diaminodi.- ploy, for example, diphenyl guanidine or naphphenylmethane, p,p'-diamino-dipheny1 urea and thyl biguanide. Whereas in some cases these p-aminobenzylaniline, the tri-biguanides obcompounds are suitable precipitating agents. for 10 tained from 1,3,5-triamino benzene and leucorosdyes in silver halide emulsions, they have been aniline or the tetra-biguanide obtained from found to be deficient in so i'ar as the insoluble tetra-aminmditolymethane. precipitates have a remarkable tendency to be The compounds,-which the said biguanides form dissolved during alkaline after treatment of the v with a great number of soluble acid dyes used for exposed layers. Furthermore, the employment of color photographic purposes, are insoluble in biguanides or dibiguanides to-increase the rewater andin every case the water-solubility of sistance against water or diazotypes has already the compound formed from an acid dye and a been describedbiguanide derived from an aromatic diamine or It has now been found that the condensation polyamine is less than the water-solubility o! the products obtainable from dicyandiamide and arocompound formed from the same acid dye and matic dior poly-amines are especially useful for the biguanide derived from the correspondingv fixin Sol d dyes in light-sensitive silver aromatic monoamine. Furthermore, whereas halide emulsions or in filter layers used adjacent most of the compounds formed from acid dyes to silver halide emulsions. These reaction prodand biguanides derived from aromatic monoucts can be prepared by the method described by amines are soluble in the usual alkaline photo- Cohn in the "Journal fiir Praktische Chemie, graphic treating baths. most ofthe compo s Series 2, Volume p es 394-409 and are beformed from acid dyes and the biguanides derived lieved to lon to the group of amino-biguanides, from aromatic diamines or polyamines and, dibiguanides or p y-biguanides. pecially those derived from such compounds con- The present invention therefore consists in the so taining at least two phenyl radicals, are insoluble employment of the said biguanides, dibiguanides in and resistant to the usual alkaline photop y-biguanides derived from aromatic polygraphic treating baths.

amines as precipitating agents for acid dyes or The following table shows that the comp unds 11 y mponents in the production of a 001- formed from a number of acid dyes with biguaored light-sensitive multilayer material compris 36 nides derived from aromatic monoamines are I r B so Chloramine Red ertra M New essr as mm No. Biguanido derivative 01- I a b a b o b a b Aniline a-naphthylamine.

-nsphthylamme Pheuetidine m-Phenylendiamine a-lghenylltelrlidliamine na endiam enziinei f 'lolidine Dianisidine p, '-Diaminodi henyl-methane. ins

michlorbenzid ine p, p'-Diaminodiphenyl-urea Q.

Annalvu'nom Usrp.-c. stL-easily ol bl s0.-solubles. so.=sl ht] soluble; a. ins-almost insoluble; inn-insoluble. y 3 5332; i i gffi "12 the dyes are references to ch ltz Farbstoiitabellen, m1 ed., vol. II in the canoe! Nos. preceded v r sea. I I I 8 at least one silver halide emulsion layer and nearly all soluble in water and alkaline solutions at least one soluble acid dye in said silver halide (see- Nos. 1-4) whereas the comp formed 911111181011 -yer or in a non-sensitive lay'er adjafrom the same acid dy h hm derived cent thereto-a filter layer, for example, from aromatic diamines or 90157811111193 "4' against water and b denotes the behaviour of the same salt against a 4% sodium carbonate solution.

cording to the invention are used for precipitating dye components are shown below, the dye component used as an example being aminobenzoyl-aminobenzoyl-H-acid. The precipitates obtained by treating this compound with the dibiguanides of Benzidine,

m-Dichlorobenzidine. Tolidine, Diaminodiphenylmethane,

are all practically insoluble.

To facilitate their incorporation into the photographic layers or into the solutions and emulsions used in the preparation of such layers, the

said amino-biguanides. dibiguanides and polybiguanides are best employed in form of soluble derivatives thereof, such as, for example, the

. acetates.

In the following examples, some of the biguanides which can be used according to'this invention with advantage with soluble acid dye substances or soluble dye compounds which are fast to water and to alkaline developing solutions are set forth.

Exampl 1 4-aminodiphenyl-4'-biguanide of the following formula nmOQNn-o-Nn-o-NB,

' in in can 'be used to-advantage. This compound was.

prepared by Georg Cohn, Journal filr Praktische Chemie (2) vol. 84, page 406, year 1911 and transformed into its acetate.-

Example 2 p-Dimethylaminobenzyl- (p-tolyl) -biguanide of the following formula CHI may also be used. The compound can be prepared as follows: 24 grams of dimethylamino- The results obtained when the precipitants acaseaou benzyl-toluidine (prepared according to German Patent 108,064; Friedlaender vol. 5, page 86) are dissolved in 100 ochydrochloric acid (2n). To the boiling solution are added 9 g. dicyandiamide and after 30 further 2 g. dicyandiamide are added. During the boiling further hydrochloric acid (2n) is added to maintain a Congo acid reaction. After boiling for one'hour the solution is allowed to cool. The base is precipitated byaddition of NaOH, separated from the mother liquor and washed with water. The semi-solid oily base is dissolved in such a quantity of diluted acetic acid as to give a neutral solution and filtered from undissolved parts. The concentration of biguanide acetate in this solution is determined by the precipitation of a dye solution of known strength.

Example 3 2 (o- Biguanido-m-xylyl)-p-toluylbiguanide hydrochloride of the following formula CHa-O-NCHQ Example 4 Diphenyl-dibiguanido-propane is a further illustration of a material to be used according to this invention. It has the formula Q CHPCHEIQ In making it, 4.5 grams diphenyl-trimethylenedlamine (prepared according to M. .Scholtz, Berichte der deutschen Chemischen Gesellschaft, v01; 32, page 2252, year 1899) are dissolved in '20 cc. hydrochloric acid (2n).j To the boiling solution 5 g. dicyandiamide are added and the boiling continued fortwo hours. After cooling an excess of a 25% NaOH solution is added. From the strongly. alkaline solution the biguanide separates as'an oil. It is purified by extraction with n-butylaloohol, separated from the aqueous layer and precipitated by addition of ether. The oil soluble in water and aqueous acids.

Eaiample 5 p.p'.-Dibiguanido-dibenzyl of the formula is also useful. In making the compound p,p'- diaminodibenzyl was heated with -dicyandiamide in hydrochloric acid solutionror four hours. By addition of concentrated hydrochloric acid and cooling, the hydrochloride of the dibiguanide separates in crystalline form. It is filtered ofi, washed with NaCl solution and dried. It is easily soluble in water.

Example 6 3-biguanido carbazol of the probable formula Nll--("3NH (|TNH,

NH NH is another substance suitable for use according to the invention. In making it, 9 grams of 3-aminocarbazole are boiled with 9 g. dicyandiamide (2 mol) in 50 cc. hydrochloric acid (2n) for one. hour. Further 2 g. dicyandiamide and 50 cc.

hydrochloric acid. are added and the boiling iscarbonate solutions than compounds derived from monamines such for example as the simple phenylbiguanide, i. e.. the dyes Congo redand Pontamine Fast Blue 6GL precipitate only with an excess of phenylbiguanide and these precipitates are easily soluble in water or in a NazCOa solution of 4% strength. The precipitates of said dyes with the precipitants described in the above examples are insoluble in water and insoluble in Na2CO solution of 4% strength.

Colored photographic materials may be prepared with substances as above described for instance in the following manner:

A. 28 ccsuof a 3% aqueous solution of the dye Tuchechtbrillantrot 2B (Schultz Farbstofftabellen, 7th ed.. vol. II, page 221) and 8.5 ccs. of a 10% aqueous solution of 2,2-dichlor-4,4-dibiguanido-diphenyl-diacetate are incorporated into 100 ccs. of an ordinary silver halide gelatin emulsion. The whole is thoroughly mixed at 45 C. and the resultant emulsion is used for the reddyed light-sensitive layer of a multilayer material.

The 2,2-dichlor4,4'dibiguanido-diphenyl-diacetate used in the foregoing example as precipitant for the acid dye is prepared by condensing m-dichlorbenzidine and dicyandiamide in an aqueous medium in presence of hydrochloric acid, treating the precipitate formed with sodium hydroxide solution to obtain the free base and converting the latter into the acetate by treatment with acetic acid.

B. To cc. of silver halide gelatin emulsion are added l. A solution of 0.1 gram Diazo Light Yellow (Schultz Farbstoiftabellen 7th edition, No. 749) in 8 cc. water. l

2. A solution of 0.2 gram diphenyl-dibiguanido propane (prepared according to Example 4) in 2 cc. water containing 0.06 cc. glacial acetic acid. These two solutions are added to the emulsion Therefore, the

- group consisting of amino, substituted amino,

at a temperature of 40 C. with all precautionsto avoid formation of grains. This emulsion is coated on an area of 1000 square centimeters and thereon an ordinary gelatin layer is coated. After the exposure, development and fixing of the silver image the material is coupled with phenylmethylpyrazolone. A yellow dye is formed in the lower (silver) gelatin layer, the gelatin layer coated thereon remaining colorless.

Layers containing the insoluble compounds according to the invention are especially useful for photographic multilayer materials because, for example, the dye fixed in a filter layer does not diffuse into the. adjacent silver halide emulsion layer nor will the dye fixed in a silver halide emulsion layer diffuse into the adjacent lightsensitive or filter layers.

What is claimed is: Y

1. A light-sensi ive photographic multilayer material comprising a plurality of superimposed colloid layers, at least one of said layerscomprising a light-sensitive silver halide emulsion, and one of said layers comprising a compound formed with a, soluble acid dye substance and a material selected from the group consisting of biguanides having the following general formula:

' NCNHCNH1 A[ I II II :l

R NE NH 2 wherein R stands for a. substituent selected from the group consisting of hydrogen and hydrocarbon radicals and A stands for a substituent containing at least one basic radical selected from the guanidino, substituted guanidino and heterocyclic radicals containing at least one N-atom and :1: stands for a whole number integer.

2. A light, sensitive photographic multilayer material comprising a plurality of superimposed colloidlayers, at least one. of said layers comprising a light-sensitive silver halide emulsion, and one of said layers comprising a soluble acid dye and a precipitating agent'for the dye, said precipitating agent comprising a substance selected from the group consisting oi biguanides having the following general formula:

clic radicals containing at least one N-atom and a:

stands for a whole number integer.

3. A light sensitive photographic multilayer material comprising a plurality of superimposed colloid layers, at least one of said layers comprising a light-sensitive silver halide emulsion and one of said layers comprising a soluble acid dye forming substance'and a precipitating" ager'i't" for the dye forming substance, said precipitating agent comprising a. substance selected from'the group consisting of biguanides having the following general formula:

- N-C-NHC-NH: A--[ I II I! 1 R NH NH I wherein R stands for a substituent selected from the group consisting of hydrogen and hydrocarbon radicals and A stands for a substituent containing at least one basic radical selected from the group consisting of amino, substituted amino.

guanidino, substituted guanidino and heterocyclic radicals containing at least one N-atom and :1: stands for a whole number integer.

n 4. A light sensitive photographic multilayer 'materialcomprising a plurality of superimposed colloid layers, at least one of saidlayers comprising a light-sensitive silver halide emulsion, and one of said layers comprising a compound formed the following general formula: v

A [N-s-nn-s-Nm],

it 1&3: z V wherein R stands for a substituent selected from the group consisting of hydrogen and hydrocarrbon radicals and A stands for a substituent containing at least one basic radical. selected from the group consisting of amino, substituted'aminm' guanidino, and substituted guanidino and heterocyclic radicals containing at least one N-atom and 2: stands for a whole number integer;

- 5. A light-sensitive photographic 'multilayer I material comprising a plurality of superimposed colloid layers, at least one of said layers compris-.

ing a light-sensitive silver halide emulsion and a compound formed with a soluble acid dye and a substance having the following general formula:

wherein R stands for a substituent selected from assess? from the group consisting oi compounds having with a soluble acid dye and a substance having the following general formula:

ri-s a wherein R stands for a substituent selected from the group consisting of hydrogen and hydrocarbon radicals, A stands for an amino substituted diphenyl residue, and. :c stands'for a whole number integer.

' "I. A light-sensitive photographic multilayer material comprising a plurality of superimposed colloid layers, at least one of said layers compristhe group. consisting of hydrogen and hydrocarbon radicals and A stands for a substituent containing at least one basic radical selected from the group consisting of amino, substituted amino,

' guanidino,-substituted guanidino andheterocyclic cipitating agent comprising a substance selected I ing a light-sensitive silver halide emulsion, and one of said layers comprising a soluble acid dyeand a precipitating agent for the dye, said precipitatingagent comprising a substance selected fromthe group consisting of compounds having the following general formula:

wherein R stands'ior a substituent selected from the group consisting of hydrogen and hydrocarbon radicals, A stands for an amino substituted ben'zyl residue, and 2': stands for a whole number' integer.

8. A light-sensitive photographic multilayer material comprising a plurality of superimposed colloid layers, at least one of said layers compris ing a light-sensitive silver halide emulsion, and

one of said layers comprising a soluble acid .dye and a precipitating agent for the dye, said precipitating agent comprising asubstance selected.

from the group consisting of compounds having the following general formula:

wherein R stands 'ior a substituent selected from the group consisting oi -hydrogen and hydrocarbon radicals, A stands-for an, amino substituted diphenyl methane residuegand a; stands for a whole number integer. I v

PAUL DREYFUSiS. 

